Divergent electrochemical carboxylation of vinyl triflates: new electrochemical synthesis of phenyl-substituted α,β-unsaturated carboxylic acids and aliphatic β-keto carboxylic acids

Abstract

Electrochemical carboxylation of vinyl triflates using a magnesium anode, as a reactive metal electrode, was investigated. Alkyl-substituted vinyl triflates were electrolyzed in the presence of an atmospheric pressure of carbon dioxide to give β-keto carboxylic acids as a sole products. On the other hand, electrochemical carboxylation of phenyl-substituted vinyl triflates gave α,β-unsaturated carboxylic acids exclusively. These divergent electrochemical carboxylation resulted from chemoselective cleavage of O–S or C–O bond of vinyl triflate, which was affected by the presence or absence of phenyl substituents in the structure of starting vinyl triflates.